Alkenes are remarkably versatile motifs as they can be further functionalized by a vast array of addition, reduction, and oxidation reactions. Thus their efficient synthesis is highly desired. Over the past 35 years, the Suzuki-Miyaura cross-coupling reaction has emerged as a powerful synthetic tool for the formation of carbon-carbon bonds. Herein is described the development of a one-pot two-step protocol for the synthesis of (E)-alkenes comprising palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl or heteroaryl halides, including chlorides, with alkenyl pinacolboronates, prepared in situ via solvent-free zirconium-catalyzed hydroboration of terminal alkynes. Avoiding isolation of intermediates saves time and reduces waste. The regio- and stereochemistry of the alkene is set by initial hydrozirconation of the alkyne. Addition of water to the second step deactivates the zirconocene catalyst, which is otherwise deleterious to cross-coupling. Thus this sequence exploits the water tolerance of the Suzuki-Miyaura reaction.
| Identifer | oai:union.ndltd.org:TORONTO/oai:tspace.library.utoronto.ca:1807/44017 |
| Date | 18 March 2014 |
| Creators | Evans, Jordan |
| Contributors | Lautens, Mark |
| Source Sets | University of Toronto |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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